Sufen Zhang

Starch-based hydrogel loading with carbendazim for controlled-release and water absorption.

Starch, with properties of eco-friendliness and abundance, is one of the most important natural polymers. Starch-based hydrogels were investigated as carriers of carbendazim to combine controlled-release and water absorption (WA). Three carbendazim-loaded hydrogels (CLHs) with different WA capacities were prepared by solution polymerization. The CLHs were characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and liquid-chromatography mass-spectrometry (LC-MS/MS). Release kinetics of CLHs was investigated using (14)C-labeling method. The diffusion parameters of CLHs were 0.47, 0.57 and 0.81 in deionized H2O (ddH2O). WA affected release profile significantly, the release longevity reaching 240 h when WA was 800 g/g in ddH2O. Solution pH influenced release profiles and the lowest release rate occurred in the lowest pH. Addition of CLH (1.3g/kg soil) markedly increased water-holding capacity (WHC) of soil by 8.2%. The study indicated that starch-based CLH was a good controlled-release agent for carbendazim and water absorbent for soil.

Stereoselective uptake and distribution of the chiral neonicotinoid insecticide, Paichongding, in Chinese pak choi (Brassica campestris ssp. chinenesis)

Neonicotinoid chiral insecticidal Paichongding is a promising substitute for the widely used imidacloprid. Four stereoisomers of Paichongding, 5R,7R, 5S,7S, 5S,7R and 5R,7S, were employed in both foliage and roots of Chinese pak choi to investigate their stereoselective uptake and distribution in pak choi. Results showed that after foliar application, no stereoselective absorption into pak-choi plants was observed among the enantiomers. Total absorptions were 35.40% of the applied amount for 5R,7R, 36.66% for 5S,7S, 36.80% for 5S,7R and 38.20% for 5R,7S at 96 HAT. The translocation of the four absorbed stereoisomers within pak choi occurred both acropetally and basipetally and the transport of (14)C from enantiomers 5R,7R and 5S,7S were significantly higher than for 5R,7S and 5S,7R. Significant stereoselective translocation inside plants was observed between Paichongding epimers. Total root uptake reached 16.49-19.85% for 5R,7R and 5S,7S, and 24.57-28.82% for 5S,7R and 5R,7S at 144 HAT. Both enantioselective and diastereoselective root uptake into pak-choi occurred between the four stereoisomers. The 5R,7S and 5S,7R enantiomers were more readily uptaken by the roots than 5R,7R and 5S,7S and accumulated in the edible leaves. These results will help to develop an understanding of Paichongding using only the target-active enantiomer of pesticides.

Enantioselective Uptake and Translocation of a Novel Chiral Neonicotinoid Insecticide Cycloxaprid in Youdonger (Brassica campestris subsp. Chinensis)

For a novel potential commercial chiral pesticide, an independent study on the fate characteristics and residues of each stereoisomer is essential if the application rates for the pesticide and human exposure are to be reduced. The absorption and translocation behavior of a chiral insecticide, cycloxaprid, in plants treated by root immersion and blade smearing was studied using (14)C-labeling tracer techniques. With the root treatment, total absorption of (1R;8S)-cycloxaprid (RS) (12.39%) was much greater than that of (1S;8R)-cycloxaprid (SR) (3.31%) at 192 h after treatment (HAT). The mass concentrations (RS/SR) of cycloxaprid in the roots, cotyledons, leaf 1, leaf 2, and leaf 3 were 37.0/16.8, 8.3/2.8, 11.7/6.5, 5.1/4.8, and 8.0/4.7 mg kg(-1) (fresh weight), respectively, at 192 HAT at an initial concentration 1.6 mg kg(-1). With the foliar application treatment, no significant difference was observed between the total absorption of RS (3.11%) and SR (4.03%) at the end of the treatment. Both acropetal and basipetal transport of absorbed (14)C occurred and more than 71.83% of absorbed RS and 82.42% of SR remained in the treated leaf. Stereoselective absorption was observed during root uptake but not during foliar absorption.

Fate of pyribambenz propyl (ZJ0273) in anaerobic soils revealed by position-specific 14C labeling

Pyribambenz propyl, or ZJ0273, is a new and widely used pyrimidynyloxybenzoic herbicide; however, its behavior and safety in anaerobic soils remain poorly understood. In this study, ZJ0273 was labeled with (14)C on its benzoate-, pyrimidyl- and benzyl- rings respectively, and applied to anoxic flooding soils to characterize its anaerobic fates. Over the 100 d incubation, the amended (14)C-ZJ0273 was slightly mineralized to (14)CO2 (<4%) or redistributed into the overlaying water (<10%), with the majority of the (14)C (82-98%) remaining in the soil. The residues in soil underwent a gradual transformation from extractable residues (ER) to bound residues (BR), with the percentage of (14)C-BR increasing from 1.1 to 2.5% at day 5 to 23.2-47.2% at day 100. The proportion of (14)C-ER, (14)C-BR and (14)CO2 depended both on the soil property and the labeling position. Generally, ZJ0273 has the highest tendency to form BR in fluvio-marine yellow loamy soil, and the mineralization on both the benzoate and benzyl rings tends to be more extensive in red-clayed soil than the other soils. The ring-specific labeling (14)C on three aromatic rings respectively provides full molecular information and yield information on sub-molecular level, i.e., the benzoate ring was generally more susceptible to cleavage than the pyrimidyl or benzyl rings (P<0.01).

Bioaccumulation and bound-residue formation of (14)C-decabromodiphenyl ether in an earthworm-soil system.

Decabromodiphenyl ether (DecaBDE) is one of the most frequently detected flame retardants in terrestrial environments. However, the fate of DecaBDE and its transport in an earthworm-soil system with and without a DecaBDE-degrading strain have rarely been evaluated. In this study, 14C-DecaBDE was self-synthesized, and a DBDE-degrading strain, Rhodococcus erythropolis, was used in an earthworm-soil system. DecaBDE showed limited degradation and mineralization after 35days of all treatments. The bound-residue (BR) formation in soil was <2.5% in the system containing earthworms, which was significantly higher (p<0.05) than that observed in the absence of earthworms (<0.45%). DecaBDE could be adsorbed by the earthworms with a BSAF of ≤0.31. The distribution of 14C-DecaBDE concentrations in the earthworm roughly followed the pattern of crop gizzard>digestive system>head>tail>body wall, suggesting that DecaBDE was mainly uptaken through ingestion. Up to 31% of the 14C-DecaBDE in the earthworms was not extractable, revealing that the total concentration of accumulated 14C-DecaBDE was underestimated. The results also showed that the presence of DecaBDE-degrading bacteria did not significantly affect the fate of DecaBDE and its accumulation in earthworms. The study indicates that the conventional assessment of the bioaccumulation and ecological effects of DecaBDE, which is based only on extractable concentrations, may underestimate the risks.

Effects of superabsorbent polymers on the fate of fungicidal carbendazim in soils.

Superabsorbent polymers (SAPs) have been extensively used as soil amendments to retain water, and they often coexist with pesticides in agricultural fields. However, effects of SAPs on the fate of pesticides in soil remain poorly understood. In this study, a laboratory experiment was conducted to evaluate the effects of SAPs on the transformation of 14C-carbendazim in soils. The results showed that compared to the SAPs-free control, 11.4% relative reduction of 14C-carbendazim extractable residue was observed in red clayey soil with SAPs amendment after 100days of incubation (p<0.05). Carbendazim dissipation was enhanced by 34.7%, while no obvious difference was found in loamy soil and saline soil (p>0.05). SAPs changed the profiles of major metabolites (2-aminobenzimidazole and 2-hydroxybenzimidazole) to some extent. After 100days of SAPs treatment, the mineralization of 14C-carbendazim was significantly reduced by 37.6% and 41.2% in loamy soil and saline soil, respectively, relative to the SAPs-free treatment (p<0.05). SAPs increased the bound residue of carbendazim by 11.1-19.1% in comparison with SAPs-free controls. These findings suggest SAPs amendments significantly affected the fate of carbendazim and attention should be given to the assessment of environmental and ecological safety of pesticides in SAPs-amended soils.

Statistical performance analysis of strict priority and generalised processor sharing two-stage scheduling system under exponentially bounded burstiness input model

Two-stage scheduling system with multiple arrival flows is widely used in many quality of service guarantee occasions. However, there is no effective, versatile method to get the performance results for this more complex service rule system. This paper analyses a two-stage scheduling system with strict priority and generalised processor sharing scheduling discipline. By using a vertical decomposition solution method, the statistical performance bounds on the backlog and delay of each flow are derived under the exponentially bounded burstiness input model. Using a discrete time Markov-modulated On–Off process example, the performance bound results are analysed.

Superabsorbent hydrogels coating increased degradation and decreased bound residues formation of carbendazim in soil

The intensive use of pesticides has caused serious environmental pollution and ecological issues. Thus, it is imperative to explore an efficient way to minimize the pesticide residues and pollution. In the present study, we employed the superabsorbent hydrogels (SHs)-coated pesticide 14C-carbendazim (H-14C-MBC) to investigate the fate of MBC in aerobic soils and to assess the soil microbial state during incubation. The results showed that after coating with SHs, MBC dissipation was improved significantly by 34.2-54.1% compared with that in the control (p<0.05), reducing the persistence of MBC in soil matrix. At 100d, the release of 14C-CO2 was enhanced by 68.0% and 46.6% in neutral loamy soil and basic saline soil, respectively, with respect to the control, resulting in more complete degradation and detoxification of MBC. Additionally, the bound residue in soils, which was associated with potential environmental risk and pollution, was reduced by 15.2% and 14.2%, respectively, compared with that in control soils. The microbial diversity of post-H-14C-MBC soil varied, and microbial composition and abundance remained different from the control, even with the refreshment of soil stability and fertility compared with the blank soil. These results demonstrate the environmental behavior of SHs-coated MBC in soils, and illustrate that SHs-encapsulated formulations would be a promising measure for reducing the soil-residue pollution and environmental risk of pesticides.

Degradation and metabolic profiling for benzene kresoxim-methyl using carbon-14 tracing

Benzene kresoxim-methyl (BKM) is an effective strobilurin fungicide for controlling fungal pathogens but limited information is available on its degradation and metabolism. This study explored the degradation and metabolic profiling for BKM in soils by carbon-14 tracing and HPLC-TOF-MS2 analyzing. Results indicated that 88%-98% of 14C-BKM remained as parent or incomplete intermediates after 100 days. Three main radioactive metabolites (M1 to M3, ≥90%) and three subordinate radioactive metabolites (Ma to Mc, ≤2%) were observed, along with a non-radioactive metabolite M4. The main intermediates were further confirmed by self-synthesizing their authentic standards, and BKM was proposed to degrade via pathways including: 1) the oxidative cleavage of the acrylate double bond to give BKM-enol (M1); 2) the hydrolysis of the methyl ester to give BKM acid (M2); 3) the cleavage of M1 and M2 to yield Mc, which could be decarboxylated to give M3; and 4) the ether cleavage between aromatic rings to form M4. This study builds a solid metabolic profiling method for strobilurins and gives a deeper insight into the eventual fate of BKM by demonstrating its transformation pathways for the first time, which may also be beneficial for understanding the risks of other analogous strobilurins.